SAXS and WAXD study of periodical structure for polyacrylonitrile fiber during coagulation

Small angle X‐ray scattering (SAXS) and wide angle X‐ray diffraction (WAXD) were adopted to investigate the formation and development of high order structure within polyacrylonitrile (PAN) precursor during coagulation. The scattering signal came from the microvoids and long period structure was separated reasonably by the analog computation method of decomposition of the one‐dimensional profile. Based on the established methodology, the statistic parameters of long period structure, such as length of the long period structure, crystalline region and amorphous region, were obtained by the analysis of correlation function. The results indicated that during the coagulation, the length of long period of the nascent coagulated fiber was 56.1 nm (meridional direction) and 35.6 nm (equatorial direction), respectively. The evolution of the long period during the coagulation was also discussed by combining WAXD data. With the processing of coagulation, the long period was decreased since the crystallinity increased. Copyright © 2014 John Wiley & Sons, Ltd.     

Fe3O4@Nico@Ag纳米催化剂催化硝基芳烃加氢（英文）

We report the fabrication and characterization of a magnetically recyclable Fe3O4@Nico@Ag catalyst for reduction reactions in the liquid phase. Fe3O4 is a magnetic core and nicotinic acid was used as the linker for Ag. The characterization was done with X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, vibrating sample magnetometry (VSM), and ultraviolet-visible spectroscopy. VSM measurements proved the super-paramagnetic property of the catalyst.     

O2‐mediated dehydrogenative amination of phenols

A method was developed for the direct dehydrogenative construction of C? N bonds between unprotected phenols and a series of cyclic anilines without resorting to any kind of metal activation of either substrate and without the use of halides. The resulting process relies on the exclusively organic activation of molecular oxygen and the subsequent oxidation of the aniline substrate. This allows the coupling of ubiquitous phenols, thus furnishing aminophenols through an atom‐economical and most sustainable dehydrogenative amination method. This new reactivity, which relies on the intrinsic organic reactivity of cumene in what can be seen as a modified Hock activation process of oxygen, is expected to have a large impact on the formation of C? N bonds in organic synthesis.     

Direct electrochemical oxidation of a pesticide, 2,4-dichlorophenoxyacetic acid,at the surface of a graphite felt electrode: Biodegradability improvement

Pesticides’ biorecalcitrance can be related to the presence of a complex aromatic chains or of specific bonds, such as halogenated bonds, which are the most widespread. In order to treat this pollution at its source, namely in the case of highly concentrated solutions, selective processes, such as electrochemical processes, can appear especially relevant to avoid the possible generation of toxic degradation products and to improve biodegradability in view of a subsequent biological mineralization. 2,4-D was found to be electroactive in oxidation, but not in reduction, and the absence of hydroxyl radicals formation during the electrochemical step was demonstrated, showing that the pretreatment can be considered as a “direct” electrochemical process instead of an advanced electrochemical oxidation process. The presence of several degradation products in the oxidized effluent showed that the pretreatment was not as selective as expected. However, the relevance of the proposed combined process was confirmed since the overall mineralization yield was close to 93%.     

Utilization of photocatalysts in decarboxylative coupling of carboxylic N-hydroxyphthalimide (NHPI) esters

Recently, the visible-light photoredox decarboxylative couplings of N-(acyloxy)phthalimides (NHPI esters) and its derivatives have become an efficient chemical transformation. Under visible light, the NHPI esters undergo a single-electron transfer (SET) process to afford the corresponding carbon or nitrogen radicals that participate in many chemical transformations. The photoredox decarboxylative couplings have been applied to achieve construction of an array of carbon–carbon and carbon–heteroatom bonds as well as the synthesis of carbocycles and heterocycles. This review categorises photocatalysts, discusses the application and catalysis mechanisms of NHPI esters, and details recent progress in this field.     

Efficient and green oxidation of alcohols with tert-butyl hydrogenperoxide catalyzed by a recyclable magnetic core-shell nanoparticle-supported oxo-vanadium ephedrine complex

A novel method for the oxidation of alcohols to the corresponding carbonyl compounds has been successfully developed using tert-butyl hydrogenperoxide (TBHP) in the presence of a catalytic amount of recyclable magnetic nanoparticle-supported oxo-vanadium ephedrine complex (VO(ephedrine)₂@MNPs) in PEG as a green solvent at 80 °C. The catalyst can be magnetically recycled and successfully reused in six subsequent reaction cycles with only slight decreases of its catalytic activity.     

Dynamics of milling processes with variable time delays

A milling-process model with a variable time delay associated with each cutting tooth is presented in this article. The source of this variable time delay is the feed rate. The effect of the feed motion on the entry cutting angle, the exit cutting angle, and the amplitude of feed mark is also discussed. Loss-of-contact effects are also considered. The system dynamics is described by a set of delay differential equations with periodic coefficients and variable time delays. A semi-discretization scheme is presented for analyzing the stability of periodic orbits of this system. The analysis provides evidence of period-doubling bifurcations and secondary Hopf bifurcations. Good agreement is found between the numerical results obtained from this work and the results of related experimental studies.     

Beitrag zur Prüfung metallischer Werkstoffe im Torsionsversuch

Zusammenfassung Der Torsionsversuch eignet sich zur Untersuchung des plastischen Verhaltens von Metallen bei erhöhten Temperaturen, wenn die Fließspannung stark von der Umformgeschwindigkeit abhängt. Aus der gemessenen Drehmoment-Drehwinkel-Kurve wird die Fließkurvek _f () berechnet. Hierfür wird ein Fließkriterium benötigt, dessen Unsicherheit im allgemeinen größer ist als alle Meßfehler. Diese Unsicherheit geht aber nicht in die berechnete Dehngeschwindigkeitsempfindlichkeit ein, die somit als Hauptergebnis des Versuches anzusehen ist.Um die Bedingungen technischer Warmumformung zu simulieren, wird die Verwendung extrem kurzer Proben (flacher Scheiben) empfohlen, womit sehr hohe Umformgeschwindigkeiten erreicht werden können. Für die Auswertung derartiger Versuche ist die wirksame Länge der kurzen Proben — experimentell oder semiempirisch — zu bestimmen und die Kerbwirkung zu berücksichtigen. Im Gegensatz zur herkömmlichen Vorgehensweise wird empfohlen, die örtliche Spannung und Verzerrung nicht für die Mantelfläche der Probe zu berechnen, sondern für einen kritischen Radialabstand im Innern der Probe, für den die Schiebung von der Kerbwirkung unabhängig ist, so daß sich die zuverlässigsten Werte ergeben.

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Summary The torsion test is often used for studying the plastic deformation of metals at elevated temperatures when stress depends strongly on the strain rate. From the measured torque-twisting angle curve, the stress-strain curvek _f () has to be calculated. For this purpose a yield criterion has to be used the uncertaintly of which normally exceeds all experimental errors. This uncertaintly, however, does not propagate into the calculated strain rate sensitivity which therefore may be considered as the main result of the torsion test.For simulating the conditions of technical hot forming processes, the use of extremely short test pieces (flat discs) by which very high strain rates can be obtained is recommended. For evaluating the test data the efficient lenght of short specimens has to be determined. In opposition to the conventional procedure of test evaluation, it is recommended not to calculate stress and strain for the surface of the specimen but for a critical radius for which strain is independent of the notch effect so that the most reliable values are obtained.

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